Method for reducing CO2, CO, NOX, and SOx emissions

ABSTRACT

Industrial combustion facilities are integrated with greenhouse gas-solidifying fertilizer production reactions so that CO 2 , CO, NO x , and SO x  emissions can be converted prior to emission into carbonate-containing fertilizers, mainly NH 4 HCO 3  and/or (NH 2 ) 2 CO, plus a small fraction of NH 4 NO 3  and (NH 4 ) 2 SO 4 . The invention enhances sequestration of CO 2  into soil and the earth subsurface, reduces N0 3   −  contamination of surface and groundwater, and stimulates photosynthetic fixation of CO 2  from the atmosphere. The method for converting CO 2 , CO, NO x , and SO x  emissions into fertilizers includes the step of collecting these materials from the emissions of industrial combustion facilities such as fossil fuel-powered energy sources and transporting the emissions to a reactor. In the reactor, the CO 2 , CO, N 2 , SO x , and/or NO x  are converted into carbonate-containing fertilizers using H 2 , CH 4 , or NH 3 . The carbonate-containing fertilizers are then applied to soil and green plants to (1) sequester inorganic carbon into soil and subsoil earth layers by enhanced carbonation of groundwater and the earth minerals, (2) reduce the environmental problem of NO 3   − runoff by substituting for ammonium nitrate fertilizer, and (3) stimulate photosynthetic fixation of CO 2  from the atmosphere by the fertilization effect of the carbonate-containing fertilizers.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with United States Government support awarded by the Department of Energy to Lockheed Martin Energy Research Corporation, Contract No. DE-ACO5-96OR22464. The United States Government has certain rights in this invention.

CROSS-REFERENCE TO RELATED APPLICATIONS

(Not Applicable)

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to chemical, geological, and photosynthetic sequestration of CO₂, pollution control systems, and particularly to a method for removal of CO₂, CO, NO_(x), and SO_(x) emissions, for reduction of NO₃ ⁻ contamination of surface water and groundwater, and for sequestration of inorganic carbon into soil and subsoil earth layers.

2. Description of the Relevant Art

The rise in anthropogenic greenhouse gas emissions, particularly CO₂, is attributed largely to the increased use of fossil fuels. Fossil fuels, particularly coal, oil, and natural gas, are the primary fuels of industrialized society. These fuels supply abundant energy at low cost. Currently 22 gigatons (Gt) of CO₂ per year (equivalent to 6 Gt C/yr) is emitted as a result of the use of fossil fuels. Coal is the fuel most widely used for the generation of electricity worldwide because it is readily available, easily transportable, and relatively inexpensive. Approximately 70% of all the electricity used in the United States is generated from coal and natural gas. Oil-derived products dominate transportation fuels. Worldwide, coal-fired power plants result in about 1.8 of the 6 Gt C/yr of CO₂ emissions. The remainder is from the use of fossil fuels in transportation, industry, and residences.

The increasing effects of CO₂ emissions and global warming have challenged the industrialized world to find new and better ways to meet the increasing need for energy while reducing greenhouse gases. A treaty recently negotiated in Kyoto, Japan, would require developed nations to reduce their emissions of greenhouse gases below 1990 levels by the year 2010. New strategies for economically controlling the emissions of greenhouse gases are therefore required.

The process of photosynthesis removes more CO₂ from the atmosphere than any other reaction. Each year, land-based green plants remove about 403 Gt CO₂ (equivalent to 110 Gt C) from the atmosphere and the oceans draw approximately 385 Gt CO₂ as well. An enhancement as small as 6% for terrestrial or ocean photosynthesis is sufficient to remove 22 Gt CO₂ (6 Gt C), or the entire amount of CO₂ emitted into the atmosphere annually from the use of fossil fuels. The requirements of the recent Kyoto Treaty could be satisfied by an increase of only 0.62% in annual global photosynthetic biomass production, if the increased biomass is in a stable form such as woody products.

In many parts of the world, land-based photosynthesis in the form of crop production is limited by the lack of fertilizers. Nitrogen in the form of ammonium, NH₄ ⁺, is the most-needed fertilizer since it is an essential substrate for the synthesis of all amino acids—and thus proteins, chlorophyll, and many lipid molecules of membranes. All are important components of photosynthetic membranes. An increase in the use of fertilization can dramatically enhance photosynthetic activity by stimulating more green plants to grow. This would result in the capture of more sunlight energy and the fixation of more CO₂. A more abundant supply of environmentally friendly fertilizers and appropriate fertilization of trees can be a positive contribution to global CO₂ sequestration.

SUMMARY OF THE INVENTION

According to the invention, industrial combustion facilities can be integrated with greenhouse gas-solidifying fertilizer production reactions so that CO₂, CO, NO_(x), and SO_(x) emissions are converted into carbonate-containing fertilizers, primarily NH₄HCO₃ and (NH₂)₂CO, that can enhance the sequestration of CO₂ into soil and the earth subsurface, reduce the problem of NO₃ ⁻ runoff, and stimulate photosynthetic fixation of CO₂ from the atmosphere. Therefore, CO₂ emission sources, such as from a fossil fuel-fired power plant, are directed to a reactor before they can be emitted through smokestacks. In the reactor, CO₂ is converted to at least one selected from the group consisting of NH₄HCO₃ and (NH₂)₂CO. The NH₄HCO₃ and/or (NH₂)₂CO is then applied into soil to enhance carbonization of soil and subsoil earth layers and to stimulate photosynthetic fixation of CO₂ from the atmosphere.

The production of NH₄HCO₃ and (NH₂)₂CO is summarized by the reactions:

2CO₂+N₂+3H₂+2H₂O →2NH₄HCO₃↓

CO₂+N₂+3H₂→(NH₂)₂CO↓+H₂O

Methane (CH₄) and/or carbon monoxide (CO) can be utilized instead of hydrogen gas according to the following reactions:

5CO₂+4N₂+14H₂O+3CH₄→8NH₄HCO₃↓

CO₂+4N₂+2H₂O+3CH₄→4(NH₂)₂CO↓

3CO+N₂+5H₂O→2NH₄HCO₃↓+CO₂

The invention is also useful for removing NO_(x) and SO_(x) emissions by the following reaction pathway:

wherein R is at least one selected from the group consisting of CO, H₂ and CH₄.

Catalysts are used to catalyze the reactions of the invention. Preferred catalysts include, but are not limited to, nanometer-structured and/or hybridized metallocatalysts of Ru, Os, W, Fe, Pt, Pd, and Ni.

Important features and advantages of the invention include the following:

1. Integration of combustion facilities with greenhouse gas—solidifying fertilizer production reactions—conversion of CO₂, CO, SO_(x), and NO_(x). emissions into carbonate-containing fertilizers (primarily, ammonium bicarbonate and urea);

2. Sequestration of CO₂ by enhanced carbonation of soil and subsoil terrains through the application of the carbonate-containing fertilizers;

3. Enhancement of photosynthetic fixation of CO₂ from the atmosphere by the technology-driven production of carbonate-containing fertilizers.

This invention utilizes waste heat from combustion facilities and converts various industrial waste gases, including CO₂, CO, H₂, CH₄, N₂, NH₃, NO_(x), and SO_(x), into commercial products, primarily fertilizers. It has the capability to solidify as much as 90% of the CO₂ from flue gas and place the carbonate-containing fertilizers into soil and subsoil earth layers, which at the same time can reduce NO₃ ⁻ contamination of surface water and groundwater. Based on the current annual world consumption of nitrogen fertilizers, as much as 315 million tons of CO₂ per year from smokestacks could potentially be placed as bicarbonate into soil by worldwide use of this invention. In addition, this invention has the potential to remove CO, SO_(x), and NO_(x) emissions and to enhance photosynthetic fixation of CO₂ from the atmosphere. Therefore, the invention also has significant value in improving energy efficiency, enhancing economic competitiveness, and reducing environmental impacts of both the fossil energy system and the fertilizer industry.

BRIEF DESCRIPTION OF THE DRAWINGS

There are shown in the drawings embodiments which are presently preferred, it being understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown, wherein:

FIG. 1 is a schematic representation of the method of the invention: integration of industrial combustion facilities (such as a fossil fuel-fired power plant) with chemical engineering processes so that substantial quantities of CO₂, SO_(x), and NO_(x) can be converted into carbonate-containing fertilizers, mainly NH₄HCO₃ and (NH₂)₂CO.

FIG. 2 is a schematic representation of some significant industrial applications of the invention: substantially simultaneous and/or selective removal of CO₂, CO, SO_(x), and NO_(x) emissions at an iron and steelmaking plant.

FIG. 3 is a schematic representation of the sequestration of CO₂ into soil, groundwater, the earth subsurface, and plant biomass by the application of carbonate-containing fertilizers according to the invention.

FIG. 4 illustrates NO₃ ⁻ runoff and NO_(x) emission caused by the current use of ammonium nitrate (NH₄NO₃) as a fertilizer.

FIG. 5 summarizes the expected benefits from the use of the invention and illustrates the concept of global reduction of CO_(2,) CO, SO_(x), and NO_(x) emissions according to the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention provides a method for reducing CO_(2,) CO, NO_(x) and SO_(x) emissions by converting these emissions into useful fertilizers. The invention can be applied to many combustion facilities that produce one or more of the following emissions: CO_(2,) CO, NO_(x) and SO_(x). In the preferred practice of this invention, combustion facilities are integrated with greenhouse gas-solidifying fertilizer production processes so that the gases are passed to a reactor before they can be emitted to the atmosphere and the waste heat from the combustion facilities can be utilized for the chemical engineering conversion processes. In the reactor, the emissions are converted into one or more of these compounds: NH₄HCO₃, (NH₂)₂CO, NH₄NO₃, and (NH₄)₂SO₄. Flue gas from combustion facilities typically contains about 15% CO₂ (v/v). According to the invention, CO₂ emission sources, such as from a fossil fuel-fired power plant 10, are directed to the reactor 14 prior to emission from the smokestack 18 (FIG. 1). In the reactor, flue-gas CO₂ is converted to NH₄HCO₃ using a fraction of H₂ or natural gas (CH₄) as in reaction (1):

5CO₂+4N₂+14H₂O+3CH₄→8NH₄HCO₃↓Δ_(r)G^(o)=−5.44 kJ/mol   (1)

This reaction is more environmentally sound than the current ammonium nitrate production process, which emits three molecules of CO₂ for the same amount of nitrogen-valued fertilizer:

3CH₄+4N₂+2H₂O+8O₂→4NH₄NO₃+3CO₂↑  (2)

These two fertilizer production reactions use the same amount of natural gas (3CH₄) and produce the same nitrogen-fertilizer value since each has eight N atoms. However, the NH₄HCO₃ production reaction (1) does not emit any CO₂. Instead, it can solidify five net CO₂ molecules and thus has the potential to be used as an effective CO₂-removal process.

The free energy change for reaction (1) is −5.44 kJ/mol. The negative standard free energy change indicates that this reaction could occur spontaneously at ambient temperature and pressure. The use of catalysts will improve the reaction rate. Preferred catalysts include, but are not limited to, nanometer-structured and/or hybridized metallocatalysts of Ru, Os, W, Fe, Pt, Pd, and Ni.

When ammonia is available, NH₄HCO₃ can be simply manufactured by an ammonia carbonation reaction, which can occur at room temperature and ambient pressure:

CO₂+NH₃+H₂O→NH₄HCO₃↓ΔG^(o)=−18.05 kJ/mol  (3)

The integration of combustion facilities with this CO₂-solidifying technology makes both ammonia (NH₃) and large quantities of cost-free CO₂ available so that large quantities of carbonate-containing fertilizers can be inexpensively produced. Calculations using published thermodynamic data showed that the standard free energy change (ΔG^(o)) for reaction (3) is −18.05 kJ/mol, which indicates that this carbonation reaction is favored thermodynamically. The thermodynamic equilibrium constant (K) is 1459 for this ammonia carbonation reaction. Consequently, this reaction can serve as an effective scrubbing process to remove as much as 90% of the CO₂ from the flue gas and produce a valuable product (NH₄HCO₃).

With addition of ammonia, ammonium bicarbonate can be optionally converted into urea at about 150° C.:

NH₃+NH₄HCO₃→(NH₂)₂CO+2H₂O  (4)

If necessary, this process reaction may also be achieved by the use of the waste heat from the power plants, because the temperature of a typical flue gas is close to 150° C.

The conversion of CO₂ emissions into NH₄HCO₃ and (NH₂)₂COcan also be achieved by the use of H₂ or CO through the following reactions (5-7):

2CO₂+N₂+3H₂+2H₂O→2NH₄HCO₃↓Δ_(r)G^(o)=−86.18 kJ/mol  (5)

CO₂+N₂+3H₂→(NH₂)₂CO↓+H₂OΔ_(r)G^(o)=−31.34 kJ/mol  (6)

3CO+N₂+5H₂O→2NH₄HCO₃↓+CO₂Δ_(r)G^(o)=−171.98 kJ/mol  (7)

The NH₄HCO₃ production reaction (5) indicates that the use of three H₂ molecules can fix two CO₂ molecules to produce two molecules of fertilizer. The use of three H₂ molecules in reaction (6) can fix one CO₂ molecule. Therefore, CO₂ solidification by NH₄HCO₃ production is twice as effective as that of (NH₂)₂COproduction. Reaction (1) indicates that the use of three CH₄ molecules can fix five CO₂ molecules, producing eight NH₄HCO₃ molecules. The urea production reaction (8) can fix only one CO₂ molecule using the same number of CH₄ molecules:

CO₂+4N₂+2H₂O+3CH₄→4(NH₂)CO₂  (8)

When CH₄ is used, therefore, CO₂ solidification by NH₄HCO₃ production is 5 times that of the urea production reaction (8).

Since these process reactions all have a negative value of Δ_(r)G^(o), thermodynamically they should be able to occur spontaneously at ambient temperature and pressure and are useful to treat certain industrial waste gases that contain significant amounts of H₂ and/or CO. For example, the iron and steelmaking industry has an H₂-rich flue gas known as blast furnace (BF) gas, which contains about 40% CO and 6% H₂ that are perfect to be used as an H₂ source to remove CO₂, CO, SO_(x), and NO_(x) emissions by the invention (FIG. 2). Basic oxygen furnace (BOF) and electric arc furnace (EAF) emissions 20 from a steelmaking process 24, coke oven gas 28 from a cokemaking process 32, and BF gas 36 from an ironmaking process 40 can all be processed in a reactor 44 to produce fertilizers according to the invention. The U.S. iron and steelmaking industry emits about 889,000 tons of CO per year from its sinter plant windboxes and BOFs. By use of reaction (7), CO emissions can be converted into a valuable fertilizer and 66% of the CO₂ derived from CO could be solidified into NH₄HCO₃.

Simultaneous, selective, and/or total removal of SO_(x), NO_(x), CO, and CO₂ emissions is possible by using the method described in the invention. Flue gas of many combustion facilities also contains significant amounts of NO_(x) and SO_(x) emissions at ppm levels, which could contribute to acid rain and cause environmental damage. As illustrated in FIGS. 1 and 2, this invention is also useful for removing NO_(x) and SO_(x) emissions. By use of proper catalysts, NO_(x) and SO_(x) can be converted into HNO₃ and H₂SO₄. The preferred catalysts for these conversion processes are platinum and nickel. The acid species generated from the conversion processes can then be removed by an acid-base reaction with NH₃, an intermediate of the proposed NH₄HCO₃ and (NH₂)₂CO production process, to form additional fertilizer species, NH₄NO₃ and (NH₄)₂SO₄. Therefore, the invention is capable of simultaneous, selective, and/or total removal of SO_(x), NO_(x), CO, and CO₂ emissions. The H₂ and CH₄ used in the invention can be obtained from many suitable sources. The H₂ can be generated by photosynthetic and solar photovoltaic water splitting, in addition to steam reforming of CH₄, CO, and fuel including coal. Sources of CH₄ include natural gas, fermentation of biomass, methane hydrates from oceans, and gasification of fossil fuels. When NH₃ is available, it may be employed directly in the invention for removal of the emissions.

Enhanced carbonation of soil, groundwater, and the subsoil earth layers by application of carbonate-containing fertilizers is also possible by the method of the invention. It is known that carbonates can react with alkaline earth minerals such as calcium and magnesium and can be deposited as carbonated minerals. For example, in alkaline soils such as those in the western United States (with pH values above 7), which may contain high levels of alkaline salts such as [Ca(OH)]⁺, typically from the rising or cumulative use of groundwater, the bicarbonate HCO₃ ⁻ from NH₄HCO₃ can neutralize alkaline species and reduce salt content by forming stable species like water and calcium carbonate [reaction (9)]. Solid products like CaCO₃ are a stable form of sequestered CO₂ (FIG. 3).

HCO₃ ⁻+[Ca(OH)]⁺→H₂O+CaCO₃↓  (9)

Furthermore, carbonation of earth minerals such as calcium can occur also in acidic soils (pH 4-6), according to the following reaction:

Ca²⁺+2HCO₃ ⁻→CaCO₃↓+(H₂CO₃)aq  (10)

In this reaction, half of the bicarbonate may be sequestered as solid CaCO₃. The other half (H₂CO₃) could remain in the aqueous phase if the carbonate concentration is below its maximal solubility in water (about 40 mM) and move with soil water into subsoil earth layers. In agricultural practice, the required concentration of nitrogen fertilizer (such as NH₄HCO₃) in soil solution is approximately 10 mM, which is equivalent to about 50 kg N per hectare. Water can physically hold a maximum of about 40 mM of aqueous CO₂ at ambient temperature and pressure before a gas phase of CO₂ is formed. The maximal solubility of CO₂ in water is 39.28 mM at 20° C., although natural rainfall or air-equilibrated water contains as little as 0.014 mM of dissolved CO₂. Application of earth mineral-rich materials (such as calcium and magnesium fertilizers, mineral products, or fly ash) in conjunction with NH₄HCO₃ into deep soil is preferred to enhance storage (sequestration) of inorganic carbon, especially in acidic soils (pH 4-6) such as those in the eastern United States.

In acidic soils, use of NH₄HCO₃ and (NH₂)₂CO can provide bicarbonates, such as HCO₃ ⁻ and CO₃ ²⁻, to improve soil properties by neutralizing protons according to reaction (11):

HCO₃ ⁻+H⁺→H₂O+CO₂↑  (11)

Because CO₂ is generally heavier than air, its release from soil in the field microenvironment can beneficially enrich the CO₂ supply for photosynthesis, which occurs in green plants 48 using light energy 46 (FIG. 3). In pH-neutral soils, all of the CO₂ storage reactions (9 and 10) and the protonation reaction (11) are possible.

Agricultural use of the carbonate-containing fertilizer (NH₄HCO₃) essentially disperses the carbonates in a diluted fashion (at about 10 mM concentration levels, equivalents to 50 kg N per hectare) into the soils over a vast land area. Natural rainfall and/or irrigation could then bring the carbonates down into groundwater and the earth subsurface—a potentially huge underground reservoir for CO₂ sequestration. To accelerate the transfer of carbonates into the subsoil earth layers, it is preferred to place the carbonate-containing fertilizers into deep soil before rain and/or irrigation.

The invention also employs soil as a “smart” screening material that will retain NH₄ ⁺ but allow HCO₃ ⁻to percolate with natural rainfall and/or irrigation down into groundwater, which is often rich in alkaline mineral species such as [Ca(OH)]⁺. Therefore, the carbonates could potentially react with the alkaline species in groundwater 52 and be deposited as carbonated minerals in the subsoil earth layers 56 (FIG. 3). The reason that soils commonly have much higher retaining affinity for positively charged ions such as NH₄ ⁺ than for negatively charged species such as HCO₃ ⁻ is that soil particles carry mostly negative surface charges, which attract positively charged ions but repel negatively charged species. Therefore, when NH₄HCO₃ is placed into soil, only its NH₄ ⁺ can bind with soil by replacing other cations such as Na⁺ and H⁺ on the soil particles—leaving free HCO₃ ⁻ and the exchanged cations (Na⁺, H⁺, etc.) in mobile water that could go down into subsoil earth layers. For this reason, when NH₄NO₃ is used as a fertilizer, its NO₃ ⁻ can easily “run off” with water from soils 60, resulting in not only the loss of the fertilizer but also the NO₃ ⁻ contamination of groundwater (FIG. 4). However, if NH₄HCO₃ and (NH₂)₂CO (which contain no nitrate but instead harmless carbonates) are used as fertilizers, the result can be very different—and potentially beneficial. Unlike NO₃ ⁻, carbonates (e.g., CO₃ ²⁻ and HCO₃ ⁻) are harmless species, and carbonated groundwater would not cause health problems.

Movement of groundwater can carry carbonates further down to the earth subsurface as deep as 500 to over 1000 meters, where they can be deposited by the carbonation reaction with minerals (FIG. 3). More importantly, in many geological areas, the residence time of groundwater 52 could be on the order of hundreds, even thousands, of years. Once the carbonates from the fertilizers enter this type of groundwater, they would not return to the atmosphere for hundreds of years even if they are not deposited as carbonated minerals and remain as free carbonates in the groundwater. Therefore, this groundwater-mediated CO₂ sequestration could potentially occur in essentially all land areas, including those with neutral and slightly acidic soils, as long as the carbonates can effectively percolate from soil with rainfalls and/or irrigation down into groundwater. The application of cations, such as Na⁺, and earth mineral-rich materials, such as calcium and magnesium fertilizers or fly ash, in conjunction with carbonate-containing fertilizers into deep soil is also the preferred practice to enhance the transfer of carbonates from soil into groundwater and the subsoil earth layers. Since this carbon deposition occurs in a diluted manner and covers a vast land area, the underground reservoir will probably not be saturated by this carbonation process for the next 100 years. Consequently, it is possible to use this invention, CO₂-solidifying fertilizer production and its product application with soil-groundwater-mediated sequestration of CO₂, for at least 100 years.

Photosynthetic fixation of CO₂ from the atmosphere is enhanced by the production of NH₄HCO₃ and (NH₂)₂CO, according to the invention. Both NH₄HCO₃ and (NH₂)₂CO are water soluble and can provide nitrogen (NH₄ ⁺) and CO₂ fertilization for plant photosynthesis. It has been demonstrated that with deep placement, the fertilization effect of NH₄HCO₃ on crops is similar to that of urea. When NH₄HCO₃ is dissolved in water, it forms ammonium ion and bicarbonate. Both are good plant foods that are immediately available for utilization:

NH₄HCO₃→NH₄ ⁺+HCO₃ ⁻  (12)

When (NH₂)₂CO is applied to soils, soil microorganisms will convert it into ammonium ions and carbonate:

(NH₂)₂CO+2H₂O →2NH₄ ⁺+CO₃ ²⁻  (13)

Soils commonly have strong binding affinity for ammonium ion (NH₄ ⁺), which prevents its loss. At the same time, NH₄ ⁺ can be absorbed directly by plants, primarily through their root system, for synthesis of amino acids, chlorophylls, etc. Since nitrogen fertilizer generally allows photosynthetic organisms to synthesize more “green machines” (photosynthetic reaction centers and enzymes), supplying NH₄HCO₃ and (NH₂)₂CO to crops not only sends the solidified CO₂ into the field, where it is supposed to be, but also “catalyzes” plant photosynthesis to fix many additional molecules of CO₂ from the atmosphere. Use of nitrogen fertilizer can typically produce about 50 kg dry biomass/1 kg N through plant photosynthesis. In the case of NH₄HCO₃, this is equivalent to 23.3 molecules of CO₂ sequestered in biomass per molecule of NH₄HCO₃ used. Production of one molecule of NH₄HCO₃ requires only 3/8 molecule of CH₄. Therefore, input of one CH₄ molecule through the use of this invention could result in sequestration of approximately 62 molecules of CO₂ by photosynthetic biomass production. Fertilization of trees could be an important option to enhance photosynthetic sequestration of CO₂. Wood has a C:N ratio of about 140:1 and is a more stable form of biomass. With a moderate fertilization efficiency (e.g., 60%), input of 1 NH₄ ⁺ molecule through tree fertilization could result in sequestration of 84 molecules of CO₂ into wood. If the increased quantity of nitrogen fertilizer (100−80=20 million tons of N per year) from the worldwide use of this invention is employed to fertilize trees (with 60% efficiency), 20 million tons of N could translate into 5280 million tons of CO₂ being sequestered into wood, which is equivalent to a 24% reduction of CO₂ emissions from the current world consumption of all fossil fuels. Therefore, fertilization of trees is a preferred practice in this aspect of the invention.

The expected benefits from the use of this invention are summarized in FIG. 5. The greenhouse gas-solidifying chemical engineering process uses components mostly from flue gas, air, and water, which are inexpensive and virtually inexhaustible. It produces no toxic materials but valuable commercial products (mainly, NH₄HCO₃ and (NH₂)₂CO) which can be sold to a worldwide market. This invention will enable the industrial combustion facilities 65 to remove greenhouse-gas emissions (to satisfy U.S. Environmental Protection Agency requirements) and produce valuable products that can be sold to farmers, making a profit. The current industrial price of quality natural gas (containing over 90% CH₄) is $3.47/1000 ft³ in the United States. Therefore, utilization of $28.38 of CH₄ can convert 1000 kg of CO₂ to 1800 kg of NH₄HCO₃ according to reaction (1). For its nitrogen value alone, 1800 kg of NH₄HCO₃ should sell for at least $159.30. Farmers need fertilizers to grow crops, and the growing world population needs agricultural products including foods, cotton, and woody products. Therefore, the use of this invention—from solidification of industrial CO₂ emission into carbonate-containing fertilizers to the application of the carbonate-containing fertilizers to enhance sequestration of CO₂ into soil and subsoil terrains 66 and to stimulate photosynthetic fixation of CO₂ 68 from the atmosphere—can occur spontaneously with its natural social economic force. That is, the operation of the invented concept and process technology should not require a net expenditure to perform. Therefore, by use of this technology, removal of greenhouse-gas emissions could be achieved essentially without governmental (or public) expenditure.

Consequently, this invention is preferred over alternatives such as injection of CO₂ into the bottom of oceans, a concept that would require tax dollars to implement even if such an injection technology could be developed. Further, the invention prevents the proliferation of dangerous NH₄NO₃ fertilizers, which are currently used by terrorists to make bombs.

As described above, use of the invention can enhance photosynthetic production of biomass 68. A richer volume of global biomass also results in more foods and feedstocks; more milk and animals; more cotton and silk for clothing; and more trees 74, paper and woody products including wooden furniture, houses, and buildings 76. All of these are perfectly sequestered forms of CO₂ and free of the greenhouse effect. Some of them, such as cotton and silk clothing, papers, wooden furniture, houses, and other structures, can remain for tens and even hundreds of years, maintaining their useful functions for human society (FIG. 5). Some biomass can be used as a renewable biomass energy source 80 to substitute for fossil fuels. Current biochemical engineering technology can convert biomass such as sugar and/or grain starch to ethanol. All plant materials, including stalks, straws, roots, and leaves, can be fermented to produce methane, an important gaseous fuel and feedstock, which is also useful in the invention. The residue of biomass fermentation is largely humus, which is a stable organic carbon material that can be used as a valuable additive to improve soil quality. Humus is not readily digested by microorganisms. Consequently, the lifetime of humus in soil is much longer than that of other biomass in soil. Addition of humus not only improves soil quality, such as the ability to retain water and nutrients, but also can serve as a means of carbon storage for global CO₂ sequestration. In conclusion, use of the invention can transform many industrial greenhouse-gas emitters into a productive system that can be operated in harmony with the environment—producing economic wealth and at the same time contributing positively toward global sequestration of CO₂ and protection of clean air and water resources.

The invention can be used in a number of industrial combustion facilities.

These include, but are not limited to, fossil fuel-fired power plants, biomass-fired power plants, fossil fuel-powered manufacturing plants, steam plants, petroleum and gas refinery plants, gas flaring facilities, incinerators, cement manufacturing plants, aluminum-making plants, coke-making plants, iron-making plants, and steelmaking plants.

The invention can take other forms and embodiments without departing from the essential attributes thereof, and accordingly, reference should be made to the following claims, rather than to the foregoing specification, as indicating the scope of the invention. 

What is claimed is:
 1. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbonate-containing fertilizers, wherein said emissions are reacted to produce NH₄HCO₃ fertilizer according to the formula: 2CO₂+N₂+3H₂+2H₂O→2NH₄HCO₃↓;  and applying at least a portion of said fertilizer to soil and plants.
 2. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbonate-containing fertilizers, wherein said emissions are reacted to produce NH₄HCO₃ fertilizer according to the formula: 5CO₂+4N₂+14H₂O+3CH₄→8NH₄HCO₃↓;  and applying at least a portion of said fertilizer to soil and plants.
 3. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbon-containing fertilizers, wherein said emissions are reacted to produce (NH₂)₂CO fertilizer according to the formula: CO₂+N₂+3H₂→(NH₂)₂CO↓+H₂O;  and applying at least a portion of said fertilizer to soil and plants.
 4. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbon-containing fertilizers, wherein said emissions are reacted to produce (NH₂)₂COfertilizer according to the formula: CO₂+4N₂+2H₂O+3CH₄→4(NH₂)₂CO↓;  and applying at least a portion of said fertilizer to soil and plants.
 5. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbonate-containing fertilizers, wherein said emissions are reacted according to the following reaction pathway:

 wherein R is at least one selected from the group consisting of H₂ and CH₄; NO_(x) is at least one selected from the group consisting of NO, NO₂, N₂O, N₂O₃ and N₂O₄; and SO_(x) is at least one selected from the group consisting of SO₂ and SO₃, and applying at least a portion of said fertilizers to soil and plants.
 6. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbonate-containing fertilizers, and applying at least a portion of said fertilizers to soil and plants, wherein said fertilizers are applied in conjunction with application of at least one selected from the group consisting of calcium and magnesium fertilizers, mineral products, and fly ash to soils to enhance the formation of earth mineral carbonates according to at least one of the formulas selected from the group consisting of: HCO₃ ⁻+[Ca(OH)]⁺→H₂O+CaCO₃↓ Ca²⁺+2HCO₃ ⁻→CaCO₃↓+(H₂CO₃)aq HCO₃ ⁻+[Mg(OH)]⁺→H₂O+MgCO₃↓ Mg²⁺+2HCO₃ ⁻→MgCO₃↓+(H₂CO₃)aq.
 7. A method for reducing the emissions of industrial combustion facilities, comprising the steps of: collecting emissions from said industrial combustion facilities, reacting said emissions to form at least carbonate-containing fertilizers, and applying at least a portion of said fertilizers to soil and plants, wherein said fertilizers are applied to soils and water is then applied to bring the carbonates down into groundwater and subsoil earth layers, the carbonates being deposited at the earth subsurface by carbonation reaction with earth minerals according to at least one of the formulas selected from the group consisting of:  HCO₃ ⁻+[Mg(OH)]⁺→H₂O+MgCO₃↓ Mg²⁺+2HCO₃ ⁻→MgCO₃↓+(H₂CO₃)aq HCO₃ ⁻+[Ca(OH)]⁺→H₂O+CaCO₃↓ Ca²⁺+2HCO₃ ⁻→CaCO₃↓+(H₂CO₃)aq. 